WO2018115288A1 - Huiles de base exemptes de trouble présentant une teneur élevée en composés paraffiniques - Google Patents

Huiles de base exemptes de trouble présentant une teneur élevée en composés paraffiniques Download PDF

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Publication number
WO2018115288A1
WO2018115288A1 PCT/EP2017/084105 EP2017084105W WO2018115288A1 WO 2018115288 A1 WO2018115288 A1 WO 2018115288A1 EP 2017084105 W EP2017084105 W EP 2017084105W WO 2018115288 A1 WO2018115288 A1 WO 2018115288A1
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WO
WIPO (PCT)
Prior art keywords
solvent
paraffinic
mixture
base oils
base oil
Prior art date
Application number
PCT/EP2017/084105
Other languages
English (en)
Inventor
Eglantine Armelle Christiane Colette Marie ALBE
Godfried Johannes AARTS
José Luís MONIZ JARDIM
Cornelis Hyacinthus Maria VAN DER HULST
Ralf Gunnar MEISTER
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP17818161.6A priority Critical patent/EP3559157A1/fr
Priority to CN201780079439.XA priority patent/CN110099983B/zh
Priority to US16/471,639 priority patent/US11078430B2/en
Publication of WO2018115288A1 publication Critical patent/WO2018115288A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/28—Recovery of used solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
    • C10G61/04—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only the refining step being an extraction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/304—Pour point, cloud point, cold flow properties

Definitions

  • the present invention relates to a method for reducing the cloud point of base oils with high
  • base oils are categorised into five groups according to their sulphur content, saturates/ paraffinic content, as well as according to their viscosity index.
  • Group I base oils comprise more than 0.03% sulphur, less than 90% saturates /paraffinic content, and have a viscosity index ranging between 80 to 120.
  • Group II base oils in contrast, comprise less than
  • Group II and Group III base oils is that, Group I base oils are solvent refined, Group II base oils are hydro- treated and Group III base oils are hydro-cracked, said two processes leading to the increased saturates/ paraffinic content of Group III over Group I and Group II, and Group II over Group I.
  • Group IV base oils are polyalphaolefins, and Group V includes all base oils that do not fall within Groups I to IV.
  • Base oils can suffer from the undesirable presence of a waxy haze.
  • waxy haze is attributed often to the presence of long carbon chain paraffins, and their presence adversely affect the intended lubrication function of base oils, for example by changing their viscosity or by clogging up hardware components.
  • the waxy haze may be inferred or measured in a number of ways, for instance by according to the standard test method ⁇ ASTM D4176-04' . Whilst initially ASTM D4176-04 was set up for fuels, it is also a relevant standard test method that can be adopted for base oils, by providing a numerical rating of haze appearance.
  • hazy base oils need to have their cloud point reduced by a process of de-waxing.
  • De-waxing may be carried out by treating hazy base oils with one or more solvents, or by subjecting the hazy base oils to a chemical process where insufficiently isomerized long carbon chain paraffins that contribute to the haze are catalytically isomerized/cracked to convert them into molecules that do not attribute to any haze.
  • Solvent de-waxing has an advantage over catalytic de-waxing in that it is less complicated to carry out, for which less costly hardware maybe used.
  • WO02070627 and WO2009080681 describe exemplary processes for solvent and catalytic de-waxing.
  • Solvent dewaxing is well known to those skilled in the art and involves admixture of one or more solvents and/or wax precipitating agents with a base oil or a base oil precursor fraction, and cooling the mixture to a temperature in the range of from -10°C to -40°C,
  • the separation step such as filtration or centrifugation, to remove the precipitated wax crystals from the base oil or the base oil precursor fraction.
  • the admixture can be removed from the base oil by a process such as distillation.
  • C 3 -C 8 ketones e.g. methyl ethyl ketone (MEK) , methyl isobutyl ketone and mixtures thereof
  • C 8 -C 10 aromatic hydrocarbons e.g. toluene
  • MEK is thought to induce wax crystal formation
  • toluene is thought to reduce the viscosity of the solvent-base oil mixture, so that wax crystals may be removed by processes such as filtration or by centrifugation, which are carried out at temperatures below the cloud point of the solvent-base oil mixture.
  • toluene and other aromatic hydrocarbons are begin to be substantially insoluble in base oils with higher saturates/paraffinic content.
  • paraffinic content using MEK-toluene It is therefore an object of the present invention to provide a method for reducing the cloud point of base oils with high saturates/paraffinic content to below 0°C. It is a further objective of the present invention to provide a method for the preparation of base oils with high saturates/paraffinic content that remain 'clear and bright' at 0°C.
  • the present invention provides a method for reducing the cloud point of a base oil with high saturates/paraffinic content to below 0°C, wherein the method comprises subjecting said base oils to a cloud point reduction step comprising adding said base oil to a solvent mixture, wherein the solvent mixture comprises a paraffinic naphtha fraction and a co-solvent to obtain a solvent treatment mixture; and subjecting the solvent treatment mixture to a solvent de-waxing step.
  • the inventors of the present method have
  • the present invention concerns a method for reducing the cloud point of a base oils with high saturates/ paraffinic content to below 0°C, wherein the method comprises subjecting said base oils to a cloud point reduction step comprising (a) adding said base oils to a solvent mixture, wherein the solvent mixture comprises a paraffinic naphtha fraction and a co-solvent to obtain a solvent treatment mixture; and (b) subjecting the solvent treatment mixture to a solvent de-waxing step.
  • base oils with high saturates/paraffinic content may be base oils with more than 90% saturates/paraffinic content, such as Group II and Group III base oils (according to the API categories) .
  • base oils with high saturates/ paraffinic content may be also base oils with more than 95% saturates/paraffinic content.
  • base oils with high saturates/paraffinic content may be also base oils with 98% or more saturates/paraffinic content.
  • the base oil comprises more than 90 wt . % of paraffins and more than 90 wt . % of saturates.
  • the inventors of the present method surprisingly discovered that the cloud point of base oils with high saturates/paraffinic content can be reduced to below 0°C using a naphtha fraction.
  • the naphtha fraction is a Fischer-Tropsch process derived paraffinic fraction.
  • Fischer-Tropsch process enables the manufacture of paraffinic molecules from gaseous hydrocarbon feedstock by first breaking down the hydrocarbon feedstock to carbon monoxide and
  • fractions such as kerosene and diesel.
  • the naphtha fraction may be obtained from said atmospheric distillation, which is conventionally used to fractionate the more heavily branched iso- paraffins into, for example, kerosene and diesel.
  • the naphtha fraction that may be obtained from said atmospheric distillation comprises paraffinic molecules with boiling points less than 200°C at ambient atmospheric pressure.
  • the lower boiling point fraction comprises paraffinic molecules with boiling points between 35°C and 200°C, more preferably boiling points between 40°C and 200°C, and even more preferably boiling points between 70°C and 170°C, all boiling points being at around ambient atmospheric pressure.
  • the paraffinic naphtha fraction according to the present invention comprises less than 5 wt . % of aromatics and a content of paraffins of more than 90 wt.% according to ASTM D6839. More preferably, the paraffinic fraction comprises at least 90 wt.% paraffins, at most 5 wt.% aromatics and at most 1 wt.% olefins. Even more preferably, the paraffinic naphtha fraction
  • n-paraffins in a range of from 40 to 50 wt.%, iso-paraffins in a range of from 50 to 60 wt.%,
  • naphthenes in a range of from 2 to 3 wt.% and aromatics in a range of from 0 to 0.1 wt.%.
  • the naphtha fraction comprises paraffinic molecules comprising carbon chain length of up to 11.
  • the naphtha fraction comprises paraffinic molecules comprising carbon chain length in the range of from 5 to 11, more preferably the naphtha fraction comprises paraffinic molecules comprising carbon chain lengths of from 6 to 10, even more preferably the naphtha fraction comprises paraffinic molecules comprising carbon chain lengths of from 6 to 9, and most preferably the naphtha fraction comprises paraffinic molecules
  • naphtha fraction may be a paraffinic molecule of carbon chain length of 7, such as heptane.
  • the naphtha fraction comprises paraffinic molecules of carbon chain length of 6, 7 and 8.
  • the naphtha fraction comprises paraffinic molecules of carbon chain length of either 5, or 6, or 7, or 8, or 9, or 10, or 11.
  • the naphtha fraction comprises a mixture of any combination thereof of paraffinic molecules of carbon chain length of either 5, or 6, or 7, or 8, or 9, or 10, or 11.
  • Examples of the naphtha fraction a mixture of any combination thereof of paraffinic molecules of carbon chain length of either 5, or 6, or 7, or 8, or 9, or 10, or 11, may be for example, a paraffinic molecule of carbon chain length of 5 in a mixture comprising at least a paraffinic molecule of carbon chain length of 6, or 7, or 8, or 9, or 10, or 11; or paraffinic molecules of carbon chain length of 6 in a mixture comprising at least a paraffinic molecule of carbon chain length of 5, or 7, or 8, or 9, or 10, or 11; or paraffinic molecules of carbon chain length of 7 in a mixture comprising at least a paraffinic molecule of carbon chain length of 5, or 6, or 8, or 9, or 10, or 11; or paraffinic molecules of carbon chain length of 8 in a mixture comprising at least a paraffinic molecule of carbon chain length of 5, or 6, or 7, or 9, or 10, or 11; or paraffinic molecules of carbon chain length of 9 in a mixture comprising at least a paraffinic molecule of carbon chain length of 5, or 6, or 7,
  • the cloud point of the base oil with high saturates/paraffinic content is reduced to below 0°C.
  • the method of the present invention comprises the steps of subjecting the base oil with high
  • saturates/paraffinic content with a solvent mixture, wherein the solvent mixture comprises a naphtha fraction and a co-solvent, and subjecting the solvent treatment mixture to a solvent de-waxing step.
  • the co-solvent is methyl ethyl ketone.
  • the co-solvent may also be methyl isobutyl ketone or methyl butyl ketone or methyl propyl ketone or methyl isopropyl ketone.
  • the weight ratio of the naphtha fraction to the co-solvent in the solvent mixture is in the range of from 70:30 wt% to 30:70 wt% respectively.
  • the weight ratio of the naphtha fraction to the co-solvent in the solvent mixture may be in the range of from 60:40 wt% to 40:60 wt% respectively, and more preferably, the weight ratio of the naphtha fraction to the co-solvent in the solvent mixture may be 50:50 wt% respectively.
  • the base oil with high saturates/paraffinic content is mixed with the solvent mixture in the weight ratio range of from 1:3 to 1:6 respectively at a temperature in the range of from 20°C to 150°C to provide a solvent
  • the weight ratio in which the base oil with high saturates/paraffinic content is mixed with the solvent mixture is 1:4 respectively.
  • the temperature at which the base oil with high saturates/paraffinic content is mixed with the solvent mixture may be in the range of from 30°C to 150°C.
  • the temperature at which the base oil with high saturates/paraffinic content is mixed with the solvent mixture may be also in the range of from 40 °C to 120°C.
  • the solvent treatment mixture is cooled to below at least 0°C to obtain a mixture comprising a wax fraction and a de-waxed fraction, wherein the de-waxed fraction comprises the the base oil with high saturates/ paraffinic content and the solvent mixture.
  • the solvent treatment mixture is cooled to below -20°C to enable the formation, and removal, of wax crystals.
  • the solvent treatment mixture is cooled to below -20°C to enable the formation, and removal, of wax crystals .
  • the wax crystals are removed from the solvent treatment mixture by subjecting the solvent treatment mixture to a mechanical treatment known in the art, such as by the use of a spinning drum to undertake a
  • the solvent mixture is removed from the de-waxed fraction by a distillation step to obtain a base oil with high saturates/paraffinic content with a cloud point below 0°C.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne un procédé de réduction du point de trouble d'une huile de base présentant une teneur élevée en composés saturés/paraffiniques jusqu'à une valeur inférieure à 0 °C, le procédé consistant à soumettre lesdites huiles de base à une étape de réduction du point de trouble consistant à ajouter ladite huile de base à un mélange de solvants, le mélange de solvants comprenant une fraction de naphta paraffinique et un co-solvant, pour obtenir un mélange de traitement aux solvants ; et à soumettre le mélange de traitement aux solvants à une étape de déparaffinage aux solvants.
PCT/EP2017/084105 2016-12-23 2017-12-21 Huiles de base exemptes de trouble présentant une teneur élevée en composés paraffiniques WO2018115288A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP17818161.6A EP3559157A1 (fr) 2016-12-23 2017-12-21 Huiles de base exemptes de trouble présentant une teneur élevée en composés paraffiniques
CN201780079439.XA CN110099983B (zh) 2016-12-23 2017-12-21 具有高链烷烃含量的无浑浊基础油
US16/471,639 US11078430B2 (en) 2016-12-23 2017-12-21 Haze-free base oils with high paraffinic content

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16206786.2 2016-12-23
EP16206786 2016-12-23

Publications (1)

Publication Number Publication Date
WO2018115288A1 true WO2018115288A1 (fr) 2018-06-28

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PCT/EP2017/084105 WO2018115288A1 (fr) 2016-12-23 2017-12-21 Huiles de base exemptes de trouble présentant une teneur élevée en composés paraffiniques

Country Status (4)

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US (1) US11078430B2 (fr)
EP (1) EP3559157A1 (fr)
CN (1) CN110099983B (fr)
WO (1) WO2018115288A1 (fr)

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US20200087581A1 (en) 2020-03-19
CN110099983A (zh) 2019-08-06
US11078430B2 (en) 2021-08-03

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